JP5587519B1 - Dam material composition for image display device and image display device using the same - Google Patents

Abstract

A dam material composition capable of making it difficult to discriminate a seam, in addition to having a cured product having an appropriate hardness and adhesion to an adherend as a dam material, and An image display device using the same is provided.
(A) A polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom, having a viscosity at 23 ° C. of 20 to 25000 cP; (B) (B1) A linear polyorganosiloxane containing saturated groups and optionally (B2) SiO _4/2 units, R ′ ₃ SiO _1/2 units and R ′ ₂ SiO _2/2 units, and optionally further R′SiO a _three / ₂ units, per molecule, at least three R 'is an aliphatic unsaturated group, and a branched polyorganosiloxane, the polyorganosiloxane containing an aliphatic unsaturated group; (C) A photoinitiator; (D) a silane compound containing an aliphatic unsaturated group; and (E) a fumed silica having a BET specific surface area of 180-500 m ² / g, wherein (B ) And (D), the ratio of the number of mercaptoalkyl groups present in (A) to the total number of aliphatic unsaturated groups in the range from 0.45 to 1.50, and (E) is (B ) Dam material composition for an image display device having 0.5 to 24 parts by weight with respect to 100 parts by weight and having a viscosity at 23 ° C. of 20,000 to 10,000,000 cP, and image display thereof Display device used for sealing between the portion and the protective portion.
[Selection figure] None

Description

  The present invention relates to a dam material composition for an image display device and an image display device using the same.

  In recent years, attention has been focused on flat panel image display devices such as liquid crystal, plasma, and organic EL. A flat panel type image display device usually has a large number of pixels composed of a semiconductor layer, a phosphor layer, or a light emitting layer constituting an active element between a pair of light-transmitting substrates such as glass. It has a display area (image display portion) arranged in a matrix. Generally, the periphery of this display area (image display portion) and a protective portion formed of optical plastic such as glass or acrylic resin is sealed secretly with an adhesive.

  In such an image display device, a sealant is interposed between the protection unit and the image display unit in order to prevent a decrease in visibility (visibility) due to reflection of outdoor light or indoor illumination. For example, an ultraviolet curable silicone resin composition is used as the sealant (Patent Document 1). In addition to the silicone resin composition, an epoxy resin composition may be used as a sealant (Patent Document 2).

WO2012 / 084402 JP 2002-121259 A

  However, when the above ultraviolet curable resin composition is used as an encapsulant in an image display part (for example, a liquid crystal display panel), the composition may protrude from the display part or on the back side of the display part due to its fluidity. Problems such as enveloping may occur, and in recent years when the display portion has become larger, it has become more apparent. In order to solve this problem, a method of preventing a protrusion or the like by forming a frame using a dam material composition in advance on the display unit or the protection unit and applying the composition therein is known. ing.

  Patent Document 2 discloses that a dam material is obtained by adding fine silica to an epoxy resin composition as a sealant. However, Patent Document 2 does not describe the hardness and adhesiveness of the cured product of the dam material. In addition, Patent Document 2 describes nothing about applying other resin-based sealants as dam materials.

  An object of the present invention is to provide a silicone-based dam material composition whose cured product has appropriate hardness and adhesion to an adherend as a dam material, and an image display device using the same. More preferably, in addition to this, a clear seam is generated between the frame of the dam material and the sealant therein, and the problem that visibility as an image display device may be reduced, It is an object of the present invention to provide a dam material composition and an image display device using the dam material composition that make it difficult to distinguish a joint.

（式中、
Ｒ^１は、独立して、脂肪族不飽和基であり、
Ｒは、独立して、Ｃ１〜Ｃ６アルキル基又はＣ６〜Ｃ１２アリール基であって、Ｒのうち、１〜６０モル％はＣ６〜Ｃ１２アリール基であり、
ｎは、２３℃における粘度を１００〜１，０００，０００ｃＰとする数である）で示される、脂肪族不飽和基を含有する直鎖状ポリオルガノシロキサンと、場合により（Ｂ２）ＳｉＯ_４／２単位、Ｒ'_３ＳｉＯ_１／２単位及びＲ'_２ＳｉＯ_２／２単位、並びに場合によってはさらにＲ'ＳｉＯ_３／_２単位（式中、Ｒ'は、それぞれ独立して、Ｃ１〜Ｃ６アルキル基又は脂肪族不飽和基を表す）からなり、１分子当たり、少なくとも３個のＲ'が脂肪族不飽和基である、分岐状ポリオルガノシロキサンとからなる、脂肪族不飽和基を含有するポリオルガノシロキサン；
（Ｃ）光反応開始剤；
（Ｄ）脂肪族不飽和基を含有するシラン化合物；並びに
（Ｅ）ＢＥＴ比表面積１８０〜５００ｍ^２／ｇの煙霧質シリカ
を含み、ここで、
（Ｂ）及び（Ｄ）中の脂肪族不飽和基の合計個数に対する、（Ａ）に存在するメルカプトアルキル基の個数の比が、０．４５〜１．５０であり、
（Ｅ）が、（Ｂ）１００重量部に対して、０．５〜２４重量部であり、かつ
２３℃における粘度が、２０，０００〜１０，０００，０００ｃＰである
画像表示装置用のダム材組成物に関する。
本発明２は、（Ｂ）中の脂肪族不飽和基の個数に対する、（Ａ）中のメルカプトアルキル基の個数の比が、０．５〜４．０である、本発明１の画像表示装置用のダム材組成物に関する。
本発明３は、（Ｄ）中の脂肪族不飽和基の個数に対する、（Ａ）中のメルカプトアルキル基の個数の比が、１．２〜３．５である、本発明１又は２の画像表示装置用のダム材組成物に関する。
本発明４は、（Ｅ）が、ＢＥＴ比表面積３００〜５００ｍ^２／ｇの煙霧質シリカである、本発明１〜３のいずれかの画像表示装置用のダム材組成物に関する。
本発明５は、ダム材組成物について、Ｂ型回転粘度計を使用して、２３℃で、回転数６ｒｐｍで測定した粘度（ｃＰ）をＶ_6rpm、２３℃で、回転数１２ｒｐｍで測定した粘度（ｃＰ）をＶ_12rpmとし、式：Ｖ_6rpm／Ｖ_12rpmにより求めたチキソトロピー比の値が、１．０５〜２．０である、本発明１〜４のいずれかの画像表示装置用のダム材組成物に関する。
本発明６は、（Ｃ）の含有量が、（Ｂ）１００重量部に対して、０．０５〜５０重量部である、本発明１〜５のいずれかの画像表示装置用のダム材組成物に関する。
本発明７は、（Ｄ）が、３−メタクリロキシプロピルトリエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン及びビニルトリエトキシシランからなる群より選ばれる１種以上の脂肪族不飽和基を含有するシラン化合物である、本発明１〜６のいずれかの画像表示装置用のダム材組成物に関する。
本発明８は、画像表示部と保護部との封止に、本発明１〜７のいずれかの画像表示装置用のダム材組成物を用いてなる、画像表示装置に関する。 This invention 1 is (A) polyorganosiloxane containing the mercaptoalkyl group couple | bonded with a silicon atom whose viscosity in 23 degreeC is 20-25000 cP;
(B) (B1) Formula (I):

(Where
R ¹ is independently an aliphatic unsaturated group;
R is independently a C1 to C6 alkyl group or a C6 to C12 aryl group, and 1 to 60 mol% of R is a C6 to C12 aryl group,
n is a linear polyorganosiloxane containing an aliphatic unsaturated group represented by the viscosity of 100 to 1,000,000 cP at 23 ° C. and optionally (B2) SiO _4/2 units, R _'3 SiO _1/2 units and R' ₂ SiO _2/2 units and further R'SiO _3/2 units (wherein optionally,, R 'are each independently, C1 -C6 alkyl group Or a branched polyorganosiloxane having at least three R's each of which is an aliphatic unsaturated group, and a polyorgano having an aliphatic unsaturated group. Siloxane;
(C) a photoinitiator;
(D) a silane compound containing an aliphatic unsaturated group; and (E) a fumed silica having a BET specific surface area of 180-500 m ² / g, wherein
The ratio of the number of mercaptoalkyl groups present in (A) to the total number of aliphatic unsaturated groups in (B) and (D) is 0.45 to 1.50,
Dam material for an image display device in which (E) is 0.5 to 24 parts by weight with respect to 100 parts by weight of (B) and the viscosity at 23 ° C. is 20,000 to 10,000,000 cP Relates to the composition.
The present invention 2 is the image display device of the present invention 1, wherein the ratio of the number of mercaptoalkyl groups in (A) to the number of aliphatic unsaturated groups in (B) is 0.5 to 4.0. The present invention relates to a dam material composition.
In the image 3 of the present invention 1 or 2, the ratio of the number of mercaptoalkyl groups in (A) to the number of aliphatic unsaturated groups in (D) is 1.2 to 3.5. The present invention relates to a dam material composition for a display device.
The present invention 4 relates to the dam material composition for an image display device according to any one of the present inventions 1 to 3, wherein (E) is a fumed silica having a BET specific surface area of 300 to 500 m ² / g.
The present invention 5 uses the B-type rotational viscometer for the dam material composition, and the viscosity (cP) measured at 23 ° C. and 6 rpm is measured at V _{6 rpm} and 23 ° C. and 12 _rpm . The dam material for an image display device according to any one of the present inventions 1 to 4, wherein (cP) is V _{12 rpm} , and the value of the thixotropy ratio determined by the formula: V _{6 rpm} / V _{12 rpm is 1.05} to 2.0. Relates to the composition.
Invention 6 is a dam material composition for an image display device according to any one of Inventions 1 to 5, wherein the content of (C) is 0.05 to 50 parts by weight with respect to 100 parts by weight of (B). Related to things.
In the present invention 7, (D) is at least one aliphatic group selected from the group consisting of 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. It is related with the dam material composition for image display apparatuses in any one of this invention 1-6 which is a silane compound containing a saturated group.
This invention 8 relates to the image display apparatus which uses the dam material composition for image display apparatuses in any one of this invention 1-7 for sealing with an image display part and a protection part.

  The present invention is a dam material composition, and when an image display device is produced using the dam material composition, the frame formed from the dam material composition has an appropriate hardness and adhesion to an adherend. is there. More preferably, it is difficult to distinguish a seam between the frame of the dam material and the sealant therein, and an image display device having good visibility can be provided.

The dam material composition for the image display device of the present invention is
(A) A polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom, having a viscosity at 23 ° C. of 20 to 25000 cP;
(B) (B1) Formula (I):

(Where
R ¹ is independently an aliphatic unsaturated group;
R is independently a C1 to C6 alkyl group or a C6 to C12 aryl group, and 1 to 60 mol% of R is a C6 to C12 aryl group,
n is a linear polyorganosiloxane containing an aliphatic unsaturated group represented by the viscosity of 100 to 1,000,000 cP at 23 ° C. and optionally (B2) SiO _4/2 Units, R ′ ₃ SiO _1/2 units and R ′ ₂ SiO _2/2 units, and optionally further R′SiO _3/2 units (wherein R ′ is independently a C1-C6 alkyl group, Or a branched polyorganosiloxane having at least three R's each of which is an aliphatic unsaturated group, and a polyorgano having an aliphatic unsaturated group. Siloxane;
(C) a photoinitiator;
(D) a silane compound containing an aliphatic unsaturated group; and (E) fumed silica having a BET specific surface area of 180 to 500 m ² / g.

  The composition of the present invention comprises (A) a polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom, which has a viscosity at 23 ° C. of 20 to 25000 cP.

  In (A), the number of mercaptoalkyl groups bonded to silicon atoms in one molecule is, on average, 2 or more and 20 from the viewpoint of suppressing excessive curing shrinkage while ensuring a stable structure by a crosslinking reaction. It can be as follows. Among these, more than 2 and 10 or less are preferable, and more preferably 3 to 7.

  In (A), the alkyl portion of the mercaptoalkyl group bonded to the silicon atom can be a C1-C6 alkyl group. Examples of the mercaptoalkyl group include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, 4-mercaptobutyl, 6-mercaptohexyl and the like. From the viewpoint of ease of synthesis, mercaptomethyl, 3-mercaptopropyl, etc. Is preferred, and 3-mercaptopropyl is more preferred.

  In (A), the organic group other than the mercaptoalkyl group bonded to the silicon atom can be a substituted or unsubstituted monovalent hydrocarbon group (provided not to be an aliphatic unsaturated group). . Specifically, an alkyl group, such as a C1-C6 alkyl group (for example, methyl, ethyl, propyl, etc.); a cycloalkyl group, such as a C3-C10 cycloalkyl group (for example, cyclohexyl, etc.); an aryl group, for example, C6-C12 Aryl groups (eg, phenyl, tolyl, xylyl, etc.); aralkyl groups, eg, C7-C13 aralkyl groups (eg, 2-phenylethyl, 2-phenylpropyl, etc.); substituted hydrocarbon groups, eg, halogen-substituted hydrocarbon groups (eg, , Chloromethyl, chlorophenyl, 3,3,3-trifluoropropyl, etc.). An alkyl group is preferable from the viewpoint of easiness of synthesis, etc. Among them, methyl, ethyl and propyl are preferable, and methyl is more preferable. In order to adjust the refractive index, an aryl group can be used in combination, and among them, phenyl is preferable from the viewpoint of ease of synthesis.

The structure of the main chain of (A) may be linear, branched or cyclic, and is preferably branched. For example, R ″ SiO _3/2 units, R ″ ₃ SiO _1/2 units and R ″ ₂ SiO _2/2 units, and optionally further SiO _4/2 units (where R ″ is Each independently composed of an unsubstituted or substituted monovalent hydrocarbon group (provided not to be an aliphatic unsaturated group), 2 or more and 20 or less R ′ per molecule Examples thereof include branched polyorganosiloxanes containing mercaptoalkyl groups, wherein 'is a mercaptoalkyl group. Examples of the mercaptoalkyl group and the unsubstituted or substituted monovalent hydrocarbon group include the groups described above. R ″ which is a mercaptoalkyl group may be present as R ″ of any unit, but is preferably present as R ″ of R ″ SiO _3/2 unit. As the mercaptoalkyl group and the unsubstituted or substituted monovalent hydrocarbon group, the above groups can be applied. From the viewpoint of workability and crosslinking reactivity, the ratio of the number of siloxane units containing a mercaptoalkyl group to the number of siloxane units not containing a mercaptoalkyl group is preferably 1:60 to 1: 5, but is not limited thereto. .

  In (A), the viscosity at 23 ° C. is 20 to 25000 cP. From the viewpoint of workability and refractive index, for example, the viscosity can be set to 30 to 23000 cP. From the viewpoint of compatibility and workability, the viscosity at 23 ° C. can be, for example, 20 to 2000 cP, and more preferably 50 to 500 cP.

  In the present specification, the viscosity is measured with a B-type rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.) using a rotor No. 2 to 4 are used, and the values are measured at 30 to 60 rpm and 23 ° C. (however, regarding the number of revolutions, if there is a separate description, it shall be followed).

The number of mercapto groups in (A) can be measured by colorimetric titration with iodine. This is the following formula:
2RSH + I ₂ → RSSR + 2HI
This method utilizes the fact that the titration solution becomes slightly yellow with a small amount of excess iodine during titration.

  (A) is preferably highly transparent. As an index of transparency, at 23 ° C., when (A) was filled in a container, and the transmittance at a visible light region wavelength (360 to 780 nm) was measured with a spectrophotometer for a thickness of 10 mm, It is mentioned that the transmittance is 80% or more. The transmittance is preferably 90% or more from the viewpoint that the transparency of the cured product of the composition of the present invention can be stably maintained.

  The method for preparing (A) is not particularly limited. For example, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethylmethoxysilane, mercaptopropyldimethylethoxy. It can be produced by hydrolyzing, polycondensing, and re-equilibrating an alkylchlorosilane such as silane, mercaptoalkylalkoxysilane, and a desired alkylchlorosilane, alkylalkoxysilane, or silanol-containing siloxane.

  (A) may be used alone or in combination of two or more.

  The composition of the present invention comprises (B) (B1) formula (I):

(Where
R ¹ is independently an aliphatic unsaturated group;
R is independently a C1 to C6 alkyl group or a C6 to C12 aryl group, and 1 to 60 mol% of R is a C6 to C12 aryl group,
n is a linear polyorganosiloxane containing an aliphatic unsaturated group represented by the viscosity of 100 to 1,000,000 cP at 23 ° C. and optionally (B2) SiO _4/2 Units, R ′ ₃ SiO _1/2 units and R ′ ₂ SiO _2/2 units, and optionally further R′SiO _3/2 units (wherein R ′ is independently a C1-C6 alkyl group, Or a branched polyorganosiloxane having at least three R's each of which is an aliphatic unsaturated group, and a polyorgano having an aliphatic unsaturated group. Contains siloxane.

  In (B), (B2) is an optional component and can be blended for the purpose of adjusting the hardness of the cured product. By using (B2) in combination, the adhesion can be improved, particularly when the adherend is a polarizing plate. For example, (B2) is the total number of aliphatic unsaturated groups in (B). It can be used in such an amount that the proportion of the number of aliphatic unsaturated groups in (B2) is 20 to 85%. The ratio of the number of aliphatic unsaturated groups in (B2) is preferably more than 50% from the viewpoint of fast curability, and can be, for example, 60 to 85%, more preferably 65 to 85%. .

In formula (I) for (B1), R ¹ is an aliphatic unsaturated group. R ^{1 at} both ends may be the same or different, but is preferably the same.

  Aliphatic unsaturated groups include alkenyl groups such as C2-C6 alkenyl groups (eg, vinyl, propenyl, butenyl, hexenyl, etc.). An alkenyl group having an unsaturated terminal is more preferable, and a vinyl group is preferable from the viewpoint of ease of synthesis.

  In the formula (I), R is a C1-C6 alkyl group (for example, methyl, ethyl, propyl, etc.) or a C6-C12 aryl group (for example, phenyl, tolyl, xylyl, etc.). R may be the same or different.

  From the viewpoint of adjusting the refractive index, 1 to 60 mol% of R is a C6 to C12 aryl group, and from the viewpoint of viscosity and thixotropy, 1 to 50 mol% of R is a C6 to C12 aryl group. It is preferable that it is 1 to 35 mol%.

  From the viewpoint of ease of synthesis and the like, the C1-C6 alkyl group is preferably methyl, and the C6-C12 aryl group is preferably phenyl.

  As (B1), in formula (I), 1-60 mol% of R is a phenyl group and the remainder is a methyl group, more preferably 1-50 mol% of R. Is a phenyl group and the remainder is a methyl group, more preferably 1 to 35 mol% of R is a phenyl group and the remainder is a methyl group.

  (B1) has a viscosity at 23 ° C. of 100 to 1,000,000 cP, more preferably 1000 to 1,000,000 cP, and still more preferably 3000 to 500,000 cP from the viewpoint of workability of the composition. Those having a high viscosity are not preferable because an unnecessarily high value is not preferable because the remaining material remains in the form of a thread from the tip of the discharge port after application of the composition, and the member is easily soiled when the tip is moved. From the viewpoint of ejection properties that greatly affect the productivity of products using the composition and shape retention after ejection, a particularly preferred viscosity range is 15,000 to 300,000 cP.

  The number of aliphatic unsaturated groups in (B1) can be determined from the molecular weight obtained by calculating the average structural formula by NMR, calculating the molecular weight.

  The method for preparing (B1) is not particularly limited, and for example, polycondensation and re-equilibration of chlorosilanes necessary for a desired structure such as dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, dimethylvinylchlorosilane, and the like is performed. Alternatively, it can be obtained by cohydrolyzing alkoxysilanes necessary for a desired structure such as dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, dimethylvinylmethoxy, etc., and performing polycondensation and re-equilibration reactions. it can. In addition, 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane, 1,1,3,3,5,5,7,7-octaphenylcyclotetrasiloxane, 1,1, Siloxanes necessary for a desired structure such as 3,3-tetramethyl-1,3-divinyldisiloxane can be converted to an alkali catalyst (alkali metal hydroxide, alkali metal silanolate, ammonium hydroxide, etc.) or acid catalyst (sulfuric acid). , Silanolate sulfate, trifluoromethanesulfonic acid) in the presence of ring-opening polymerization and re-equilibration.

  (B1) may be used alone or in combination of two or more.

(B2) is SiO _4/2 unit, R ′ ₃ SiO _1/2 unit and R ′ ₂ SiO _2/2 unit, and optionally further R′SiO _3/2 unit (wherein R ′ is It is a branched polyorganosiloxane consisting of a C1-C6 alkyl group or an aliphatic unsaturated group and having at least three R's per molecule as an aliphatic unsaturated group.

As (B2), with respect to 1 mol of R ′ ₂ SiO _2/2 units, a branched form having a ratio of 6 to 10 mol of SiO _4/2 units and 4 to 8 mol of R ′ ₃ SiO _1/2 units. Polyorganosiloxane is mentioned. (B2) is preferably a solid or viscous semi-solid resinous or liquid at room temperature. Examples include those having a weight average molecular weight of 1,000 to 400,000, preferably 2,000 to 200,000. The weight average molecular weight is a value obtained by using polystyrene as a calibration curve by gel permeation chromatography (GPC).

Examples of the aliphatic unsaturated group for R ′ include the groups listed as the aliphatic unsaturated group in (B1), and specifically include alkenyl groups such as C2 to C6 alkenyl groups (eg, vinyl, propenyl, butenyl). Hexenyl, etc.). An alkenyl group having an unsaturated terminal is more preferable, and a vinyl group is preferable from the viewpoint of ease of synthesis. R ′ which is an aliphatic unsaturated group may be present as R ′ of any unit, but is preferably present as R ′ of the R ′ ₂ SiO unit.

  R ′ other than the aliphatic unsaturated group is a C1-C6 alkyl group (for example, methyl, ethyl, propyl, etc.), and a methyl group is preferable in consideration of heat resistance.

  When (B2) is used, it may be used alone or in combination of two or more.

  The composition of the present invention comprises (C) a photoinitiator. (C) is a component that functions as a radical initiator or a sensitizer when photocrosslinking (A) and (B). (C) is an aromatic hydrocarbon, acetophenone and derivatives thereof, benzophenone and derivatives thereof, o-benzoylbenzoic acid ester, benzoin and benzoin ether and derivatives thereof, xanthone and derivatives thereof, disulfide compounds, quinones. Examples include compounds, halogenated hydrocarbons and amines, and organic peroxides. From the viewpoint of compatibility with silicone and stability, a compound or an organic peroxide containing a substituted or unsubstituted benzoyl group is more preferable.

  Examples of (C) include acetophenone, propiophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651: manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR 1173: manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184: manufactured by BASF), 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE 2959: manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (IRGACURE 127: manufactured by BASF), 2-methyl-1- (4-methylthio) Enyl) -2-morpholinopropan-1-one (IRGACURE 907: manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369: manufactured by BASF) ), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (IRGACURE 379: manufactured by BASF); 6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN TPO: manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819: manufactured by BASF); 1,2-octanedione , 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (IRGACURE OXE 01: manufactured by BASF), ethanone, 1- [9-ethyl-6 (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02: manufactured by BASF); oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxy Ethoxy] ethyl ester, oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester mixture (IRGACURE 754: manufactured by BASF), phenylglyoxylic acid methyl ester (DAROCUR MBF: manufactured by BASF), ethyl-4- Dimethylaminobenzoate (DAROCUR EDB: manufactured by BASF), 2-ethylhexyl-4-dimethylaminobenzoate (DAROCUR EHA: manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphos Fin oxide (CGI 403: manufactured by BASF), benzoyl peroxide, kume Peroxide, and the like.

  (C) may be used alone or in combination of two or more.

  The composition of the present invention comprises (D) a silane compound containing an aliphatic unsaturated group. (D) plays the role which improves the adhesiveness and adhesiveness to the base material of hardened | cured material. Examples of the aliphatic unsaturated group include the groups listed as the aliphatic unsaturated group in (B1), specifically, alkenyl groups such as C2-C6 alkenyl groups (for example, vinyl, propenyl, butenyl, hexenyl, etc.). ). An alkenyl group having an unsaturated terminal is more preferable, and a vinyl group is preferable from the viewpoint of ease of synthesis.

  Examples of (D) include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane, preferably 3-methacryloxypropyltriethoxysilane, 3- Methacryloxypropyltrimethoxysilane.

  (D) may be used alone or in combination of two or more.

The composition of the present invention contains (E) fumed silica having a BET specific surface area of 180 to 500 m ² / g. By blending (E), a viscosity suitable for dam formation can be obtained, and thixotropy can be imparted. Furthermore, the composition of the present invention has a high viscosity of 20,000 cP or more, and generally there is a concern that the wettability is lowered and the adhesiveness of the cured product is poor. Nevertheless, by properly blending the component (E), the cured product of the composition of the present invention exhibits good adhesiveness, but the blend of (E) contributes to this. I understood.

The BET specific surface area of the fumed silica is 180 to 500 m ² / g. By using a material in this range, it is possible to impart the necessary thixotropy to the composition in a small amount, and accordingly, a composition with higher transparency can be easily obtained. From the viewpoint of transparency, preferably from 200 to 500 m ² / g, more preferably 300~500m ² / g. Further, when formulating those exceeding 500 meters 2 / ^g, the load is applied to the kneading operation and the like on the preparation method, since the appearance tends to lump of stones or the like tends to occur flame, 500 meters 2 / ^g or less of those Is preferred.

  The fumed silica includes not only surface-treated fumed silica but also surface-treated fumed silica. The surface treatment can improve compatibility and increase the thixotropy. Examples of the surface treatment include treatment with chlorosilane (methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc.), alkoxysilane, hexamethyldisilazane, octamethylcyclotetrasiloxane, dimethylsiloxane oligomer, and the like. In particular, treatment with hexamethyldisilazane is preferable from the viewpoint of transparency. These surface treatment agents may be blended with kneaded silica at the time of preparation of the composition of the present invention, and kneaded to perform silica surface treatment.

  (E) may be used alone or in combination of two or more.

  The number of mercaptoalkyl groups bonded to the silicon atom in (A) is HS, the number of aliphatic unsaturated groups in (B) is ViB, and the number of aliphatic unsaturated groups in (D) is ViD. The ratio of HS to ViB + ViD (HS / (ViB + ViD)) is 0.45 to 1.50, preferably 0.50 to 1.30, from the viewpoint of imparting appropriate hardness and elasticity to the cured product. Yes, more preferably from 0.60 to 1.20. When only (B1) is used as (B), the number of aliphatic unsaturated groups in (B) is equal to the number of aliphatic unsaturated groups ViB1 in (B1), while (B1) and When (B2) is used in combination, the number of aliphatic unsaturated groups in (B) is the number of aliphatic unsaturated groups ViB1 in (B1) and the number of aliphatic unsaturated groups in (B2) ViB2. It becomes the sum of.

  Moreover, from the point which provides favorable adhesiveness and suppresses the temperature change of hardened | cured material, it is preferable that ratio (HS / ViB) of HS with respect to ViB is 0.5-3.5, 0.95 More preferably, it is -3, More preferably, it is 1-2.

  From the point of further improvement of good adhesiveness and suppression of temperature change of the cured product, the ratio of HS to ViD (HS / ViD) is preferably 1.2 to 3.5, and preferably 1.5 to 3. More preferably, it is 1.8 to 2.5.

  From the viewpoint of photoreaction initiation action, heat resistance during curing, and visibility (high transmittance and low haze), (C) is preferably 0.05 to 50 parts by weight with respect to (B) 100 parts by weight. More preferably, it is 0.1 to 40 parts by weight.

  (E) can be used at 0.5 to 24 parts by weight with respect to 100 parts by weight of (B), and (E) is 1 to 23 weights from the viewpoint of improving the adhesion to the substrate. Part is preferable, and 5 to 20 parts by weight is more preferable.

  From the viewpoint of deformation resistance and visibility, the total amount of (A) to (E) is preferably 55% by weight or more, more preferably 75% by weight or more, and still more preferably 90% in the composition. % By weight or more.

  The composition of the present invention preferably further contains (F) a silicone resin adhesion improver (however, (A), (B) and (D) are excluded). The silicone resin adhesion improver refers to a silicone resin having tackiness, and is blended as necessary in order to further strengthen and stabilize the adhesive property of the ultraviolet curable silicone resin composition of the present invention. In particular, when the adherend is a polarizing plate, a high improvement effect can be expected.

  From the viewpoint of adhesiveness and economy, (F) includes at least one silicone resin selected from the group consisting of MQ resin, MDQ resin, MT resin, MDT resin, MDTQ resin, DQ resin, DTQ resin and TQ resin. Adhesive adhesion improver (but not containing aliphatic unsaturated group and mercapto group) is preferable, and is selected from the group consisting of MQ resin, MDQ resin, MDT resin and MDTQ resin from the viewpoint of fluidity and ease of synthesis. One or more silicone resin-based adhesion improvers are more preferable, and one or more silicone resin-based adhesion improvers selected from the group consisting of MQ resins, MDQ resins, and MDT resins are more preferable, and high tackiness and structure control are easy. From the viewpoint, MQ resin is more preferable.

As the MQ resin, the average structural formula is represented by the following formula _{{(CH 3) 3 SiO 1/2} } m {SiO 2} n
(Where m + n = 1, and m and n are non-zero numbers), and the MDQ resin has an average structural formula of the following formula {(CH ₃ ) ₃ SiO _{1 / 2} m {SiO 2} n} {(CH 3) 2 SiO} l
(Where m + n + 1 is 1 and m, n, and 1 are non-zero numbers), and the MT resin has an average structural formula of the following formula {(CH ₃ ) ₃ SiO _1/2 } _m {(CH ₃ ) SiO _3/2 } _o
(Where m + o = 1, m and o are non-zero numbers), and the MDT resin has an average structural formula of the following formula {(CH ₃ ) ₃ SiO _{1 1 2} } _m {(CH ₃ ) ₂ SiO} _l {(CH ₃ ) SiO _3/2 } _o
(Where m + l + o = 1 and m, l and o are non-zero numbers), and the MDTQ resin has an average structural formula of the following formula {(CH ₃ ) ₃ SiO _{1/2} m {SiO 2} n} {(CH 3) 2 SiO} l {(CH 3) SiO 3/2} o
(Where m + n + l + o = 1, and m, n, l and o are non-zero numbers). The DQ resin has an average structural formula represented by the following formula {SiO ₂ } _n {(CH ₃ ) ₂ SiO} _l
(Where n + 1 is 1 and n and l are non-zero numbers), and the DTQ resin has an average structural formula of the following formula {SiO ₂ } _n {(CH ₃ ) ₂ SiO} _l {(CH ₃ ) SiO _3/2 } _o
(Where n + l + o = 1 and n, l and o are non-zero numbers), and the TQ resin has an average structural formula represented by the following formula {SiO ₂ } _n {( CH ₃ ) SiO _3/2 } _o
(In the formula, n + o = 1, and m and o are non-zero numbers).

  The weight average molecular weight of (F) is preferably 2,000 to 100,000, more preferably 5,000 to 80,000, and still more preferably 10,000 to 60,000. Here, the weight average molecular weight is a value obtained by using polystyrene as a calibration curve by gel permeation chromatographic analysis (GPC).

  (F) can be used at 150 parts by weight or less with respect to 100 parts by weight of (B), and (F) is preferably 5 to 150 parts by weight from the viewpoint of improving the adhesion to the substrate. 10 to 120 parts by weight is more preferable, and 15 to 100 parts by weight is further preferable.

  In the composition of the present invention, the silane coupling agent (excluding (D)), inorganic fillers other than fumed silica, polymerization inhibitor, antioxidant, light resistance, as long as the effects of the present invention are not impaired. Additives such as UV absorbers and light stabilizers, which are stability stabilizers, can be blended. The composition of the present invention is a polyorganosiloxane containing an aliphatic unsaturated group other than (B) within a range not impairing the effects of the present invention (for example, a branched polyorganosiloxane containing an aliphatic unsaturated group). Can be included, but preferably is not included.

  Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropyltriethoxysilane, trimethoxysilylpropyldiallyl isocyanurate, bis (trimethoxysilylpropyl) allyl isocyanurate, tris (trimethoxysilylpropyl) isocyanurate, triethoxysilylpropyldiallyl isocyanurate, bis ( Examples include triethoxysilylpropyl) allyl isocyanurate and tris (triethoxysilylpropyl) isocyanurate.

  Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, t-butylcatechol, phenothiazine and the like.

  Antioxidants can be used to prevent oxidation of the cured product of the composition and improve weather resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine antioxidant include N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis- (2,2,6 , 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decanedioic acid) 1 (octyloxy) -4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Examples include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, etc. Examples of hindered phenol-based antioxidants include penta Erythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), N, N'-hexane-1,6-diylbis [3- ( 3,5-di-tert-butyl-4-hydroxyphenylpropioamide), benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4- Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5,5 ', 5 "-hexane-tert-butyl-4-a, a', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium Diethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine Product of 2,4,4-trimethylpentene with 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5- Triazine-2-ylamino) phenol and the like although not limited thereto. The said antioxidant may be individual or may use 2 or more types together.

  The light stabilizer can be used to prevent photo-oxidative deterioration of the cured product, and examples thereof include benzotriazole-based, hindered amine-based, and benzoate-based compounds. UV absorbers that are light-resistant stabilizers can be used to prevent light deterioration and improve weather resistance, for example, UV absorbers such as benzotriazole, triazine, benzophenone, and benzoate Etc. Examples of the ultraviolet absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4 -Benzotriazole ultraviolet absorbers such as methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(he Sil) oxy] -phenol and the like triazine ultraviolet absorbers, benzophenone ultraviolet absorbers such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. Examples include, but are not limited to, benzoate ultraviolet absorbers. The said ultraviolet absorber may be individual, or may use 2 or more types together. As the light stabilizer, a hindered amine system is preferable. Among them, it is preferable to use a tertiary amine-containing hindered amine light stabilizer for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (all of which are manufactured by BASF); MARK LA-57, LA-62, LA-67, LA-63 (all of which are Asahi) Light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Co., Ltd.).

  The composition of the present invention has a viscosity of 20,000 to 10,000,000 cP at 23 ° C. from the viewpoint of maintaining the shape after discharging in dam formation and preventing the sealant from flowing out. Here, the viscosity is a value measured at a rotational speed of 6 rpm. From the viewpoint of maintaining the shape, the lower limit is preferably 23,000 cP, more preferably 25,000 cP, and from the viewpoint of dischargeability, the upper limit is preferably 3,000,000 cP, more preferably 2,000,000 cP.

The compositions of the present invention, at 23 ° C., viscosity measured at a rotation speed 6rpm the (cP) at V _6rpm, 23 ° C., viscosity measured at a rotation speed 12rpm a (cP) and V _12rpm, with _{V 6rpm} / V _12rpm The obtained thixotropy ratio is preferably 1.05 to 2.0. When the thixotropy ratio is in this range, the discharge is easy and the shape after discharge can be maintained. The thixotropy ratio is more preferably 1.1 to 1.65, and still more preferably 1.1 to 1.6.

  The composition of the present invention can be obtained by blending (A) to (E) and optional component (F) and an additive. In preparation, after blending (B) and optional (F), blend (A), mix uniformly, and in the absence of ultraviolet rays, (C) and (D) and optional polymerization inhibitor. It is preferable to mix. For example, (A), (B), and (F) if necessary are put into a universal mixing stirrer, and mixed uniformly at room temperature (10-30 ° C.) at a low speed, and then in the absence of ultraviolet light, (C) , (D), a polymerization inhibitor, etc. are added, mixed under ice-cooling (less than 10 ° C.) at low speed, with cooling under reduced pressure, degassed, and then filtered as desired to obtain a composition. be able to.

The composition of the present invention can be cured by irradiation with ultraviolet rays. Examples of the lamp in the wavelength range of the reactive range of (C) include, for example, a high pressure mercury lamp (UV-7000), metal halide lamp (MHL-250, MHL-450, MHL-150, MHL-) manufactured by USHIO INC. 70), Korea: Metal halide lamp (JM-MTL 2KW) manufactured by JM tech, UV irradiation lamp (OSBL360) manufactured by Mitsubishi Electric Corporation, UV irradiation machine (UD-20-2) manufactured by Nippon Battery Co., Ltd. Toshiba fluorescent lamp (FL-20BLB)), Fusion H bulb, H plus bulb, D bulb, Q bulb, M bulb and the like. Irradiation dose is preferably 100~10000mJ / cm ^2, more preferably 300~5000mJ / cm ^2, more preferably from 500~3500mJ / cm ^2.

The cured product of the composition of the present invention has the following suitable physical properties.
[Visible light transmittance after curing]
Since the visible light transmittance after curing at a cured thickness of 150 μm can be 95% or more, the composition of the present invention is preferable from the viewpoint of visibility. The visible light transmittance is more preferably 96% or more, and still more preferably 98% or more. From the viewpoint of visible transmittance, it is preferable to suppress the amount of (C) used. Moreover, after mixing each component of (A) and (B) or each uniformly, the visible light transmittance after hardening can be improved by heat-processing at 80-180 degreeC. Heat treatment is preferable from the viewpoint of stability over time.

[Curing shrinkage]
Since the composition of the present invention can have a curing shrinkage rate of 1.0% or less, when applied to an image display device, distortion can be easily prevented and visibility can be ensured. Is preferable. The cure shrinkage is preferably 0.5% or less, more preferably 0.3% or less, and still more preferably 0.2% or less.

[E hardness after curing]
Since the composition according to the present invention can have an E hardness after curing of 5 to 33, when applied to an image display device, it can easily relieve stress from the outside, and has a high temperature. It is preferable in that visibility can be ensured by preventing moisture penetration even under high humidity. E hardness becomes like this. Preferably it is 5-30, More preferably, it is 10-30.

[Elongation after curing]
The composition of the present invention is preferable in that the elongation after curing can be 50% or more, which is excellent in stress relaxation from the outside and can secure deformation resistance. The elongation after curing is preferably 80% or more, more preferably 100% or more, and further preferably 200% or more.

  The composition of the present invention is a dam material composition in an image display device. The dam material composition is used to form a frame on the display unit or the protection unit of the image display device. By applying the sealant in the frame, the sealant protrudes from the display unit or the like. To prevent that. For example, the composition is trimmed on a liquid crystal panel with a dispensing nozzle of a dispensing machine (for example, 23G can be selected as appropriate according to the discharge amount), and then a material as a filler is applied and bonded to the cover panel. As a result, it is possible to prevent the filler from wrapping around the back of the liquid crystal panel and to prevent contamination of the peripheral portion. The composition of this invention has favorable adhesiveness, and can be applied suitably to both a display part or a protection part.

  The composition of the present invention is suitable for manufacturing a large screen image display device having an image display panel of 5 to 100 inches, more preferably 7 to 80 inches, and further preferably 10 to 60 inches. It is suitable for manufacturing an ultra-thin image display device having a thickness of preferably 10 to 500 μm, more preferably 20 to 450 μm, and even more preferably 50 to 400 μm.

（式中、
Ｒ^１’は、独立して、脂肪族不飽和基であり、
Ｒ'は、独立して、Ｃ１〜Ｃ６アルキル基又はＣ６〜Ｃ１２アリール基であって、Ｒ'のうち、１〜６０モル％はＣ６〜Ｃ１２アリール基であり、
ｎ'は、２３℃における粘度を１００〜２５０００ｃＰ、好ましくは１００〜８０００ｃＰとする数である）で示される、脂肪族不飽和基を含有する直鎖状ポリオルガノシロキサンと、（Ｂ２’）ＳｉＯ_４／２単位、Ｒ''_３ＳｉＯ_１／２単位及びＲ''_２ＳｉＯ_２／２単位、並びに場合によってはさらにＲ''ＳｉＯ_３／２単位（式中、Ｒ''は、それぞれ独立して、Ｃ１〜Ｃ６アルキル基又は脂肪族不飽和基を表す）からなり、１分子当たり、少なくとも３個のＲ''が脂肪族不飽和基である、分岐状ポリオルガノシロキサンとからなる、脂肪族不飽和基を含有するポリオルガノシロキサン（ただし、（Ｂ２’）の量は、（Ｂ’）中の脂肪族不飽和基の全個数に占める（Ｂ２’）中の脂肪族不飽和基の個数の割合が５０％以下となる量とする）；
（Ｃ’）光反応開始剤；及び
（Ｄ’）脂肪族不飽和基を含有するシラン化合物
を含み、ここで、
（Ｂ’）及び（Ｄ’）中の脂肪族不飽和基の合計個数に対する、（Ａ’）に存在するメルカプトアルキル基の個数の比が、０．５〜１．０５であり、
（Ｂ’）中の脂肪族不飽和基の個数に対する、（Ａ’）中のメルカプトアルキル基の個数の比が、０．９５〜３であり、かつ
（Ｄ’）中の脂肪族不飽和基の個数に対する、（Ａ’）中のメルカプトアルキル基の個数の比が、１．５〜３である、紫外線硬化型シリコーン樹脂組成物が挙げられる。 The composition of the present invention is preferred when the sealant interposed between the protective part and the image display part in the image display device is an ultraviolet curable resin composition, more preferably an ultraviolet curable silicone resin composition. This is the case of things. As the ultraviolet curable silicone resin composition used as the sealant, the composition described in WO2012 / 086402 can be used. Specifically, (A ′) the viscosity at 23 ° C. is 20 to 25000 cP. , Polyorganosiloxanes containing mercaptoalkyl groups bonded to silicon atoms;
(B ′) (B1 ′) Formula (I ′):

(Where
R ^{1 ′} is independently an aliphatic unsaturated group,
R ′ is independently a C1-C6 alkyl group or a C6-C12 aryl group, and among R ′, 1-60 mol% is a C6-C12 aryl group,
n ′ is a linear polyorganosiloxane containing an aliphatic unsaturated group represented by a viscosity at 23 ° C. of 100 to 25000 cP, preferably 100 to 8000 cP, and (B2 ′) SiO _{4. / 2} units, R ″ ₃ SiO _1/2 units and R ″ ₂ SiO _2/2 units, and optionally further R ″ SiO _3/2 units (wherein R ″ is independently C1 to C6 alkyl group or an aliphatic unsaturated group), and a branched polyorganosiloxane, wherein at least three R ″ are aliphatic unsaturated groups per molecule. Polyorganosiloxane containing a saturated group (however, the amount of (B2 ′) is the ratio of the number of aliphatic unsaturated groups in (B2 ′) to the total number of aliphatic unsaturated groups in (B ′). In such an amount that 50% or less);
(C ′) a photoinitiator; and (D ′) a silane compound containing an aliphatic unsaturated group, wherein
The ratio of the number of mercaptoalkyl groups present in (A ′) to the total number of aliphatic unsaturated groups in (B ′) and (D ′) is 0.5 to 1.05,
The ratio of the number of mercaptoalkyl groups in (A ′) to the number of aliphatic unsaturated groups in (B ′) is 0.95 to 3, and the aliphatic unsaturated groups in (D ′) An ultraviolet curable silicone resin composition in which the ratio of the number of mercaptoalkyl groups in (A ′) to the number of is 1.5 to 3 is mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise indicated, parts and% represent parts by weight and% by weight. The present invention is not limited by these examples. Curing of each composition prepared in the examples and comparative examples was made using Ushio Electric Co., Ltd .: UVL-4001M, at 120 w / cm ² and unless otherwise noted, the maximum energy dose in the curability test. (Aluminometer: UIT-250, measured by Ushio Electric Co., Ltd.) The ultraviolet energy irradiation dose was used. The maximum energy irradiation amount is an amount in which the change in E hardness of the cured product is 1 or less. Is the amount that the E hardness of the cured product ceases to change, increasing the irradiation amount in increments of 1000 mJ / cm ² , and is the larger one of the amounts in which the E hardness continues to be the same value twice? , E hardness is an amount within 1 change.

[Evaluation conditions for physical properties]
(1) Measurement of the number of mercapto groups A 1/10 normal iodine solution (special grade reagent) was used as an iodine source, and the number of mercapto groups per unit weight was determined by colorimetric titration.
Calculation method: SH content (mmol / g) = (A × P × 0.1) / (W × C)
A: Iodine solution dripping amount required until color change P: Correction coefficient of iodine solution (correction coefficient described in reagent): Described when correction is required W: Sample weight (g)
C: Non-volatile content of sample Preliminary measurement was performed to determine the amount of iodine solution, and then measured three times with high accuracy to obtain an average value of three times.

(2) Measurement of number of aliphatic unsaturated groups In NMR measurement, Si—CH ₃ (near 0.1 ppm), Si—Ph (near 7.3-7.7 ppm) and CH ₃ Si—CH═CH ₂ ( 5.7-6.3 ppm) peaks corresponding to (CH ₃ ) ₂ SiO units, Ph ₂ —SiO units and (CH ₃ ) ₂ Si—CH═CH ₂ O _1/2 units, respectively. The number of units was determined from the ratio of the respective peak intensities, the average structural formula was obtained, the molecular weight was determined therefrom, and the number of unsaturated groups was calculated.

(3) Viscosity Using a rotational viscometer (Bismetron VDA-L) (manufactured by Shibaura System Co., Ltd.), the range of 400 cP or less is No. 2 rotors are used, and the range of more than 400 to 1500 cP is No. 3 rotors are used, and the range over 1500 cP is No. Using 4 rotors, the viscosity at 23 ° C. was measured at a predetermined rotational speed. Thixotropy, the viscosity in the rotational speed 12 rpm: V _{12 rpm,} the viscosity at rpm 6 rpm: measured V _{6 rpm,} wherein: a value determined by the V _6rpm / V _12rpm.

(4) Dischargeability The composition was discharged for 10 seconds using a double threaded plastic needle (Musashi Engineering Co., Ltd .: needle length 12.7 mm, gauge: 20 G (inner diameter 0.58 mm, outer diameter 0.91 mm)). It is the weight (g).

(5) Visible light transmittance About a liquid substance, it fills a quartz cell, thickness is about 10 mm, and cured | curing material is 150 micrometers in thickness, 23 degreeC with a spectrophotometer (Minolta Co., Ltd. CM-3500d). The transmittance in the visible light region wavelength (360 to 780 nm) was measured.

(6) Curing Shrinkage The specific gravity before and after curing of the composition was measured with an electronic hydrometer (SD-120L manufactured by MIRAGE) and calculated from the difference in specific gravity of both from the following formula.
Curing shrinkage (%) = (specific gravity after curing−specific gravity before curing) / specific gravity after curing) × 100

(7) E Hardness after Curing Based on JIS K 6253 E, the energy hardness was changed by DUROMETER HARDNESS TYPE E (manufactured by ASKER), and the E hardness of the cured product at 23 ° C. was measured. E hardness after hardening is E hardness of the hardened | cured material hardened | cured with the maximum energy irradiation amount.

(8) Elongation after hardening Based on JISK6301, the elongation of the hardened | cured material hardened | cured with the maximum energy irradiation amount in 23 degreeC was measured with the shopper tensile tester (made by Toyo Seiki Seisakusho Co., Ltd.).

(9) Specific gravity The specific gravity of the cured product of the composition was measured at 23 ° C. with an electronic hydrometer (SD-120L manufactured by MIRAGE).

(10) Crack resistance and discoloration (10-1) Heat shock A 1 mm thick glass plate was applied to the entire surface so that the thickness of the composition was 200 μm, and sandwiched between 1 mm thick PMMA plates, and 3000 mJ / cm ² . After curing with an ultraviolet energy irradiation amount, an environmental test was performed in a temperature cycle from -50 ° C. to 125 ° C. (each temperature held for 30 minutes) (device name: TSA-71S-A manufactured by Espec Corp.).
Then, after returning to the state of 23 degreeC, the state of hardened | cured material, PMMA, and glass was observed with the optical microscope (10 time).
-The cured product has cracks of 0.02 mm or more in one direction and / or an air layer of 0.02 mm or more in one direction, and / or damage of 0.02 mm or more in one direction in either PMMA or glass. NG if there is,
-OK when no cracks, air layer, or damage is observed.
It was.
(10-2) Under high temperature and high humidity After leaving the cured product in a constant temperature and high humidity layer set at a high temperature and high humidity of 85 ° C. and humidity of 85% RH, a spectrophotometer (CM-3500d manufactured by Minolta Co., Ltd.) Thus, after returning to a temperature of 23 ° C. and a humidity of 50%, evaluation was performed using a yellow index which is an index of the degree of discoloration.
-If the yellow index is 1.0% or more, NG,
-OK when the yellow index is less than 1.0%
It was.

(11) Cohesive failure rate (11-1) vs. acrylic, vs. glass On each adherend (PMMA, glass) having a width of 25 mm, the composition has a thickness of 0.1 mm and a width of 25 mm and a length of 10 mm or more. A sample was prepared by coating and overlaying a tempered glass plate having a thickness of 2 mm and a width of 25 mm so that the composition had a stacking width of 10 mm, followed by curing at an ultraviolet energy dose of 3000 mJ / cm ² .
Immediately after sample preparation, samples 1 day and 3 days later were subjected to a shear adhesion test using an autograph manufactured by Shimadzu Corporation with a measurement speed of 10 mm / min to peel off the adherend and glass plate. It was.
Obtain the area Smm ² of the peeled portion of the composition on the adherend,
(100 × S) / (10 × 25)
Was calculated as the cohesive failure rate (%).
(11-2) Anti-polarizing plate As a polarizing plate, a polarizing film for liquid crystal having a width of 25 mm (product name: SEG1425DU, manufactured by Nitto Denko Corporation), an antiglare-treated film (product name: AG150, manufactured by Nitto Denko Corporation), and anti-reflection treatment were performed. A film (product name: ARS type manufactured by Nitto Denko Corporation) was prepared. Each polarizing film is applied with a width of 25 mm and a length of 60 mm or more so that the thickness of the composition is 0.1 mm, and a tempered glass plate with a thickness of 2 mm and a width of 25 mm is laminated so that the overlapping width of the composition is 10 mm. After that, it was cured at an ultraviolet energy irradiation amount of 3000 mJ / cm ² to prepare a sample. About the sample immediately after sample preparation and 2 hours later, the sample was pulled at a tensile rate of 10 mm / min using an autograph manufactured by Shimadzu Corporation, and peeled 180 ° from the polarizing film and glass plate as the adherend. A peel adhesion test was conducted.
Obtain the area Smm ² of the peeled portion of the composition on the adherend,
(100 × S) / (50 × 25)
Was calculated as the cohesive failure rate (%).
(11-3) vs. aluminum, vs. stainless steel On each adherend (aluminum, stainless steel (SUS304)) having a width of 25 mm, the composition was applied to a thickness of 0.1 mm and a width of 25 mm and a length of 10 mm or more. A tempered glass plate having a thickness of 2 mm and a width of 25 mm was overlaid so that the overlapping width of the composition was 10 mm, and then cured from the glass side with an ultraviolet energy irradiation amount of 3000 mJ / cm ² to prepare a sample.
Immediately after sample preparation, samples 1 day and 3 days later were subjected to a shear adhesion test using an autograph manufactured by Shimadzu Corporation with a measurement speed of 10 mm / min to peel off the adherend and glass plate. It was.
Measuring the area Smm ² of the release portion of the composition on the adherend was calculated cohesive failure rate (%) in the ratio of the coating area.
(100 × S) / (10 × 25)

(12) Discoloration at high temperature The cured product is stored for 500 hours under conditions of a temperature of 85 ° C. and a humidity of 85%, then returned to a state of a temperature of 23 ° C. and a humidity of 50%, and the yellow index, which is an index of the degree of discoloration, is spectrally analyzed. Evaluation was performed using a measuring instrument (CM-3500d manufactured by Minolta Co., Ltd.).

(13) Transfer performance On a slide glass (S1112) manufactured by Matsunami Glass Co., Ltd., a composition (dam material) was applied in a frame shape of 75 mm × 25 mm with a width of 0.3 mm so as to have a thickness of 200 μm. After curing with an ultraviolet energy irradiation amount of cm ² , a filling material (fill material) is applied therein, and a slide glass (S1112) manufactured by Matsunami Glass Co., Ltd. is bonded together, similarly to 3000 mJ / cm ^2. Curing was performed with an ultraviolet energy irradiation amount. The jointed part was visually observed to evaluate its visibility.
○: Not easily distinguishable by visual observation ○-△: Not easily distinguishable by visual observation △: Recognizable by visual observation Δ-X: Easy to distinguish
X: Easily distinguishable Here, the filling material was prepared as follows. The contents of (a-1), (c-1), (c-2), and (d-1) are as described later.
(A-1) 8.5 parts by weight, vinyl-terminated polymethylphenylsiloxane (viscosity 3000 cP) 79.76 weights whose end is blocked with a dimethylvinylsiloxy group, diphenylsiloxy units are 5 mol%, and the remainder is dimethylsiloxy units And 10 parts of MQ resin were mixed uniformly, then (c-1) 0.22 parts by weight, (c-2) 0.22 parts by weight, (d-1) 1.3 parts by weight were added, Furthermore, it mixed until it became uniform and it was set as the filling material. The viscosity of this material at 23 ° C. was 2750 cP (rotation speed: 60 rpm).
The MQ resin is as follows.
Average structural formula: {(CH ₃ ) ₃ SiO _1/2 } {SiO ₂ } _3.5 MQ resin Weight average molecular weight: 26200
The weight molecular weight is a value using polystyrene as a calibration curve by gel permeation chromatography (GPC).

(14) Temperature cycle adhesion test On the surface of a glass plate (1 mm thickness, 137 mm × 102 mm), a composition (dam material) is double threaded plastic needle (Musashi Engineering Co., Ltd .: needle length 12.7 mm, gauge: 23G (Inner diameter 0.33 mm, outer diameter 0.64 mm)) is applied in a frame shape of 135 mm × 100 mm with a width of 0.3 mm so that the thickness becomes 200 μm, and the filling material (fill material) is a sun ray. Using a dispenser (2300N modified) manufactured by Tec Co., coated in it, bonded to a PMMA plate (1 mm thickness, 157 mm × 110 mm), cured at an ultraviolet energy dose of 5000 mJ / cm ² , and then 23 ° C. 1 hour, then heated to 85 ° C, left at that temperature for 6 hours, then returned to 23 ° C for 3 cycles. Repeated (Equipment name: ESPEC Co., Ltd. Small Environmental Tester SU-661).
After each cycle, the state of the cured product, PMMA, and glass in the state returned to 23 ° C. was observed with an optical microscope (10 times).
-In the state where both the cured product and PPMA and glass are bonded, a crack is generated in the cured product as "crack",
-"Peeling" when peeling occurs between the cured product and at least one of PMMA and glass
It was.

(A) in an Example and a comparative example is as follows.
(A-1) Polymethylsiloxane containing a mercaptopropyl group Average structural formula: {(CH ₃ ) ₃ SiO _1/2 } {HS (CH ₂ ) ₃ SiO _3/2 } ₅ {(CH ₃ ) ₂ SiO _{2 / 2} } ₆₀
Viscosity: 330 cP
Transmittance at 10 mm thickness: 93.1%
Number of mercapto groups per unit weight: 0.97 mmol / g

(B1) in Examples and Comparative Examples is as follows.
(B1-1) Vinyl-terminated polymethylphenylsiloxane The vinyl-terminated polydimethyldiphenylsiloxane whose end is blocked with a dimethylvinylsiloxy group, 5 mol% of diphenylsiloxy units, and the remainder is dimethylsiloxy units. Aliphatic unsaturation in one molecule Average number of groups: 2
Average structural formula by NMR measurement:
_{CH 2 = CH-Si (CH} 3) 2 -O- {Si (CH 3) 2 O} 1165 - {SiPh 2 O} 61 -Si (CH 3) 2 -CH = CH 2
Viscosity: 98600 cP
Molecular weight: 98540

Synthesis of (b1-2) Vinyl-terminated polydimethyldiphenylsiloxane whose terminal is blocked with a dimethylvinylsiloxy group, 5 mol% of diphenylsiloxy units, and the remainder is dimethylsiloxy units The average number of aliphatic unsaturated groups in one molecule : 2
Viscosity: 20020 cP
Average structural formula by NMR measurement:
_{CH 2 = CH-Si (CH} 3) 2 -O- {Si (CH 3) 2 O} 595 - {SiPh 2 O} 31 -Si (CH 3) 2 -CH = CH 2
Molecular weight: 50130
The synthesis of (b1-2) was performed as follows.
A 1 L 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane was added to a 3 L separable flask equipped with a cooling reflux tube and a three-one motor as a stirrer. , 5,5,7,7-octaphenylcyclotetrasiloxane 260 g, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane 7.6 g at 150 to 160 ° C. with nitrogen gas 0.5 Nm ³ Dehydration was performed by heating and stirring at / h for 3 hours, and then 0.1 g of potassium hydroxide was added and heating and stirring was performed. Heating and stirring were continued until the potassium hydroxide dissolved and became uniform in the flask, and the viscosity increased to 15000 cP to 18000 cP. Then, after neutralizing with 10 g of ethylene chlorohydrin at 100 ° C. and filtering using super celite floss as a filter aid, the low boiling point is removed under reduced pressure of 170 to 180 ° C. and 2 mmHg. Thus, 1832 g of vinyl-terminated polymethylphenylsiloxane having a terminal blocked with a dimethylvinylsiloxy group, 5 mol% of diphenylsiloxy units, and the remainder being dimethylsiloxy units was obtained.

(B2) in Examples and Comparative Examples is as follows.
(B2-1) has an average structural formula of {(CH ₃ ) ₃ —SiO _1/2 } ₆ {SiO ₂ } ₈ {(CH ₂ ═CH) (CH ₃ ) —SiO} M ₆ D ^v Q ₈ Resin weight average molecular weight: 22450
The weight molecular weight is a value using polystyrene as a calibration curve by gel permeation chromatography (GPC).

(C) in Examples and Comparative Examples is as follows.
(C-1) 2-hydroxy-2-methylpropiophenone (c-2) 2,2-dimethoxy-1,2-diphenylethane-1-one (c-3) 1-hydroxy-cyclohexyl-phenyl-ketone

(D) in Examples and Comparative Examples is as follows.
(D-1) 3-Methacryloxypropyltrimethoxysilane

(E) in Examples and Comparative Examples is as follows.
(E-1) Hemitic silica: BET specific surface area 200 m ² / g
(E-2) Silazane (hexamethyldisilazane) -treated fumed silica: BET specific surface area 200 m ² / g
(E-3) Hemitic silica: BET specific surface area 350 m ² / g
(E-4) Silazane (hexamethyldisilazane) -treated fumed silica: BET specific surface area 350 m ² / g
(E-5) Octamethylcyclotetrasiloxane-treated fumed silica: BET specific surface area 200 m ² / g

(F-1) in Examples and Comparative Examples is as follows.
(F-1) pt-butylcatechol (polymerization inhibitor)

[Example 1]
30 parts by weight (300 g) of vinyl-terminated polymethylphenylsiloxane (b1-2) and 5 parts by weight of fumed silica (50 g) are placed in a 5 L universal mixing stirrer (manufactured by Dalton Co.) Mix evenly for 30 minutes under rotating conditions. After uniformly mixing, add 70 parts by weight (700 g) of vinyl-terminated polymethylphenylsiloxane (b1-2) and 9.5 parts by weight (95 g) of mercaptopropyl group-containing polymethylsiloxane (a-1) and mix uniformly. Then, 0.04 parts by weight (0.4 g) of pt-butylcatechol (g-1), 0.3 parts by weight of 2-hydroxy-2-methylpropiophenone (c-1) (3. 0 g), a dissolved mixture of 2,2-dimethoxy-1,2-diphenylethane-1-one (c-2) 0.3 part by weight (3.0 g), 3-methacryloxypropyltrimethoxysilane (d-1) ) 1.5 parts by weight (15 g) was added, and the mixture was uniformly mixed under cooling and reduced pressure for 30 minutes under cooling with ice water (8 ° C.) under rotation conditions with a low speed lever. Thereafter, foreign matters and the like were removed with a washed 400 mesh wire mesh to obtain a composition.

In the same manner as in Example 1, compositions of Examples and Comparative Examples were prepared with the formulations shown in Tables 1, 4 and 7, and the physical properties were evaluated. The results are shown in Tables 2-3, 5-6, and 8-9.
In addition, about Examples 2-4 and 9-12, similarly to Example 1, (b1-2) was mix | blended in 2 times by the weight ratio of 30:70.
About Examples 5-8, 13-15, 19-25, and Comparative Examples 1-2, (b1-2) is mix | blended in 2 times by the weight ratio of 30:70 similarly to Example 1, (B2-1) was blended at the same timing as the fumed silica.
In Comparative Example 3, all components (b1-2), (b2-1) and (a-1) were mixed, and then other components were added.

According to each composition of the present invention, a cured product having physical properties such as hardness and adhesiveness suitable for use in an image display device can be obtained, and it is difficult to determine the joint between the cured product and the sealant. Therefore, it is also preferable from the viewpoint of visibility.
As shown in Comparative Example 3, it can be seen that when no fumed silica having a specific BET specific surface area is blended, the adhesion and curability are poor. In addition, as shown in Comparative Examples 1 and 2, even if fumed silica having a specific BET specific surface area is blended, if the blending amount exceeds the range of the present invention, the adhesiveness is inferior and the joining performance is reduced. As can be seen, it is also inferior in terms of visibility.

  The present invention is a dam material composition, and when an image display device is produced using the dam material composition, a composition in which a frame formed from the dam material composition has appropriate hardness and adhesion to an adherend. Provided. More preferably, it is difficult to distinguish the joint between the frame of the dam material and the sealant applied therein, and an image display device having good visibility can be provided.

Claims (8)

(A) A polyorganosiloxane containing a mercaptoalkyl group bonded to a silicon atom, having a viscosity at 23 ° C. of 20 to 25000 cP;
(B) (B1) Formula (I):

(Where
R ¹ is independently an aliphatic unsaturated group;
R is independently a C1 to C6 alkyl group or a C6 to C12 aryl group, and 1 to 60 mol% of R is a C6 to C12 aryl group,
n is a linear polyorganosiloxane containing an aliphatic unsaturated group represented by the viscosity of 100 to 1,000,000 cP at 23 ° C. and optionally (B2) SiO _4/2 units, R _'3 SiO _1/2 units and R' ₂ SiO _2/2 units and further R'SiO _3/2 units (wherein optionally,, R 'are each independently, C1 -C6 alkyl group Or a branched polyorganosiloxane having at least three R's each of which is an aliphatic unsaturated group, and a polyorgano having an aliphatic unsaturated group. Siloxane;
(C) a photoinitiator;
(D) a silane compound containing an aliphatic unsaturated group; and (E) a fumed silica having a BET specific surface area of 180-500 m ² / g, wherein
The ratio of the number of mercaptoalkyl groups present in (A) to the total number of aliphatic unsaturated groups in (B) and (D) is 0.45 to 1.50,
A dam for an image display device in which (E) is 0.5 to 24 parts by weight with respect to 100 parts by weight of (B) and the viscosity at 23 ° C. is 20,000 to 2,000,000 cP Material composition.   The dam material for an image display device according to claim 1, wherein the ratio of the number of mercaptoalkyl groups in (A) to the number of aliphatic unsaturated groups in (B) is 0.5 to 4.0. Composition.   The ratio of the number of mercaptoalkyl groups in (A) to the number of aliphatic unsaturated groups in (D) is 1.2 to 3.5, for an image display device according to claim 1 or 2. Dam material composition. (E) is a fumed silica having a BET specific surface area 300~500m ² / g, the dam material composition for an image display apparatus according to any one of claims 1-3. For the dam material composition, using a B-type rotational viscometer, the viscosity (cP) measured at 23 ° C. and _{6 rpm} is V _{6 rpm} , and the viscosity (cP) measured at 23 ° C. and 12 _rpm is V and _{12 rpm,} wherein: the value of the thixotropic ratio determined by _{V 6rpm} / V 12rpmm is a 1.05 to 2.0, the dam material composition for an image display device according to any one of claims 1 to 4 .   The dam material composition for an image display device according to any one of claims 1 to 5, wherein the content of (C) is 0.05 to 50 parts by weight with respect to 100 parts by weight of (B).   (D) contains one or more aliphatic unsaturated groups selected from the group consisting of 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. The dam material composition for an image display device according to any one of claims 1 to 6, which is a silane compound.   The image display apparatus which uses the dam material composition for image display apparatuses of any one of Claims 1-7 for sealing with an image display part and a protection part.